JPH0714842B2 - Antifungal sterilization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a quaternary ammonium alginate salt, particularly a quaternary ammonium salt of alginic acid, which is hardly soluble or insoluble in water and has antifungal bactericidal properties. Regarding the method of giving.

(B) Conventional technology Various types of equipment and materials for household, industrial, medical use, whether inorganic or organic, are contaminated by microorganisms, such as growth of mold and harmful bacteria, or deterioration by microorganisms. Is happening over a wide area.

Most of the antifungal sterilization methods that have been conventionally used as a countermeasure against this problem use a water-soluble bactericide,
The bactericidal agent is eluted by water such as rainwater, and the effect of preventing the growth of mold and harmful bacteria cannot be sufficiently obtained. Therefore, effective measures are strongly demanded.

The present invention has been made to satisfy the above demands, and is a fungicide sterilization method using a quaternary ammonium salt of alginic acid as described above. It is known only and does not disclose the method of the present invention.

a) As an example of a method for producing a water-insoluble film-like acidic polysaccharide, JP-A-59-187001 discloses an aqueous solution of sodium alginate to which an aqueous solution of benzalkonium chloride of a quaternary ammonium compound is gently added. A method of forming a water-insoluble thin film of a water-insoluble benzalkonium alginate salt on the boundary surface of the is disclosed. However, a method using a solution of a quaternary ammonium salt of alginic acid as in the present invention is not disclosed, and solubility of these salts in an organic solvent is not disclosed at all.

b) West German Patent No. 1103336 discloses dimethyllaurylcetylammonium salt, abiethylammonium salt and laurylpyridinium salt of alginic acid, and German Deutsche Apoth
eker-Zeitung), Vol. 106, No. 35, 1206-1208, 1
In 966, alginic acid dodecyldimethyl, 3,4 dichlorobenzylammonium salt was disclosed, but the method of the present invention was not disclosed.

(C) Problems to be Solved by the Invention The present invention is intended to easily impart antifungal and bactericidal properties to various devices, equipment and materials.

(D) Means for Solving the Problems The inventors of the present invention have found that the quaternary ammonium salt of alginic acid obtained by reacting a quaternary ammonium compound having excellent fungicidal activity with alginic acid is poorly soluble in water. Alternatively, some are insoluble and soluble in organic solvents such as ethanol. Especially, if the solution is applied to the surface of equipment or equipment or impregnated into the material and then the solvent is volatilized and removed, excellent antifungal sterilization is achieved. Therefore, the present invention has been completed.

This invention relates to a quaternary ammonium alginate salt,
The carboxy residues of D-mannuronic acid and L-guluronic acid, which are the constituent units of alginic acid, are represented by the following formula: (In the formula, R ^{1 to} R ⁴ are each a C _1-20 linear or branched saturated or unsaturated aliphatic hydrocarbon group,
Three of R ^{1 to} R ⁴ are the above hydrocarbon groups and one is an aralkyl group,
A trialkylammonium alkyl group or an aryloxyalkyl group, two of R ^{1 to} R ⁴ are the above hydrocarbon groups and the remaining two aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or R ^{1 to} R ⁴ are one or two of the above hydrocarbon groups and the remaining two or three form a heterocyclic ring with a nitrogen atom), and are particularly water-insoluble or insoluble quaternary ammonium alginate salts. The organic solvent or a solution of a mixture of an organic solvent and a small amount of water is applied to or impregnated with an object to be imparted with antifungal sterilization property, and then the solvent is removed to prevent the object from antifungal sterilization. The present invention provides a method for preventing sterilization of mold by imparting the property.

Alginic acid is the main component of algin, a natural polysaccharide extracted from seaweed, and has a compound structure in which D-mannuronic acid and L-guluronic acid are linked in a chain.

Examples of the quaternary ammonium salt of alginic acid used in the present invention include those in which the quaternary ammonium group in the above formula is as follows.

i) R ^{1 to} R ⁴ are each a C _1-20 linear or branched, saturated or unsaturated aliphatic hydrocarbon group.

Lauryl trimethyl ammonium, cetyl trimethyl ammonium, stearyl trimethyl ammonium, trioctyl methyl ammonium, dimethyl distearyl ammonium, dimethyl oleyl linoleyl ammonium,
Trimethylmonobehenylammonium, methyltrilaurylammonium groups, etc. ii) Three of R ^{1 to} R ⁴ are the above hydrocarbon groups, one of which is aralkyl, trialkylammoniumalkyl or aryloxyalkyl.

Tetradecyldimethylbenzylammonium, (trimethylammoniumhexyl) trimethylammonium,
(Trimethyl-ammonium decyl) trimethyl ammonium [ie decametonium], lauryl phenoxy dimethyl ammonium group and the like.

iii) Two of R ^{1 to} R ⁴ are the above hydrocarbon groups and the remaining two are an aralkyl group and a dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl group.

Diisobutylphenoxyethoxyethyldimethylbenzylammonium [that is, benzethonium], (diisobutyl) methylphenoxyethoxyethyldimethylbenzylammonium group [that is, methylbenzethonium group], and the like.

iv) One or two of R ^{1 to} R ⁴ are the above hydrocarbon groups, and the remaining two or three form a heterocyclic ring with a nitrogen atom.

Laurylpyridinium, cetylpyridinium, laurylisoquinolium, laurylnicotinium, laurylquinaldium group, etc.

Preferred as the quaternary ammonium salt of alginic acid used in the present invention are lauryl trimethyl ammonium salt of alginic acid, tetradecyl dimethyl benzyl ammonium salt, cetyl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl pyridinium salt, cetyl pyridinium salt, benzethonium salt. , Methylbenzethonium salt, laurylphenoxyethyldimethylammonium salt, laurylisoquinolinium salt and the like.

The quaternary ammonium alginate salt used in the present invention is obtained by contacting and reacting at least one of alginic acid or a salt thereof (for example, a metal salt) and the corresponding quaternary ammonium compound in the form of a solution, and filtering the precipitate. It is washed with water and dried under reduced pressure at room temperature.

In particular, it is preferable to add a quaternary ammonium compound or an aqueous solution thereof to an aqueous solution of a salt of alginic acid to carry out the reaction, and this reaction can usually be carried out easily at around room temperature.

The quaternary ammonium compound is preferably obtained by maximally introducing the quaternary ammonium group into the alginic acid by using the carboxyl group of the alginic acid to be reacted in an equivalent amount or an excess amount in order to obtain strong antifungal bactericidal properties, but if desired, The reaction may be performed in an amount smaller than the equivalent amount.

Alginic acid as a raw material of the quaternary ammonium alginate used in the present invention may be, for example, a commercially available one having a molecular weight of 10,000 to 500,000, and in the case of a salt of alginic acid, an alkali metal salt such as sodium salt or potassium salt, Examples thereof include alkaline earth metal salts such as calcium salts, and sodium salts are usually preferable.

On the other hand, as the quaternary ammonium compound, a compound having antifungal bactericidal properties and, when a quaternary ammonium salt of alginic acid is formed, is dissolved in an organic solvent or an aqueous solution of an organic solvent of at least about 50% or more.

From these viewpoints, a suitable quaternary ammonium compound is a quaternary ammonium ion in the above formula combined with a halogen ion such as chlorine, bromine or fluorine ion, anion such as sulfate ion, nitrate ion or phosphate ion. Quaternary ammonium compounds may be mentioned.

The organic solvent used in the present invention is preferably one having a low boiling point because it can easily dissolve the quaternary ammonium salt of alginic acid as described above, but it is appropriately selected depending on the type and application of the quaternary ammonium salt to be dissolved. Examples thereof include lower alkyl alcohols such as methanol, ethanol and isopropanol, or acetone, toluene and benzene.

This invention, a solution of the quaternary ammonium alginate as described above dissolved in an organic solvent as described above, is applied to the surface of equipment / equipment or the like to which antifungal sterilization is to be applied, and a normal method such as vacuum drying It is carried out by removing the solvent to form a coating film of quaternary ammonium salt on the surface, or by impregnating the material to be imparted with antifungal bactericidal property and removing the solvent in the same manner as described above.

As a target for forming the coating by applying the above, a paint is applied such as an inner wall of a pure water container, an inner wall of a bathroom or the like that is liable to have a lot of moisture and mold, especially an inner wall of a reinforced concrete house where water drops easily in winter. Examples thereof include a surface or a surface without paint, such as a glass or plastic surface. It is also possible to use the quaternary ammonium salt itself as described above or the solution as described above as a mixture with the coating material applied to these surfaces.

Examples of the latter target for impregnation include paper, fibers, non-woven fabric, leather, sponge, rattan, wood, and the like, all of which can be impregnated with the organic solvent solution of the quaternary ammonium salt, and are usually less often used. Items that cannot be washed or that are difficult to wash, such as futons, tatami mats, wallpaper, wallboards, various types of sports equipment (balls for ballet and basketball, gloves for baseball, armor for kendo, etc.), furniture such as tanks Also, fungicidal properties are imparted to porous heat insulating materials, filters, books, documents, shoes and the like.

The quaternary ammonium salt content is about 0.01 to 30% depending on the desired fungicide bactericidal property. A mixture of an organic solvent and a small amount of water may be used as a solvent depending on the type of quaternary ammonium salt.

The present invention will be illustrated by the following examples, but the present invention is not limited thereto.

(E) Example Production example of quaternary ammonium salt of alginic acid To 200 g of an aqueous solution of about 2% sodium alginate, about 10% aqueous solution of each quaternary ammonium salt equivalent to a carboxyl group was added at room temperature and stirred. The formed precipitate was filtered, washed thoroughly with water, and vacuum dried at room temperature to obtain each quaternary ammonium alginate salt.

1) Sodium alginate used Kamogawa Kasei Datsukarugin NSPM 2) Quaternary ammonium compound used dodecyltrimethylammonium chloride tetradecyldimethylbenzylammonium chloride cetylpyridinium chloride benzethonium chloride benzethonium chloride The following table shows the solubility in solvents.

Bactericidal test A bactericidal test was performed on each quaternary ammonium alginate salt produced in the previous production example.

3 ml of each 0.25 g of each quaternary ammonium salt of alginic acid
Dissolve it in methanol and flow it to form a uniform thin film on the inner surface of a glass test tube with an inner diameter of 18 mm and a length of 180 mm.
A coating film of quaternary ammonium alginate was formed in the test tube by distilling methanol off under reduced pressure. A sterilization test was performed using the test tube thus obtained and a blank (untreated) test tube. Ie 10 ⁶ / ml Escherichia. Escherichia coli solution was put into a test tube, and after 30 minutes, the number of bacteria was measured by the agar plate dilution method. In the case of no treatment, there was almost no change in the number of bacteria. The number of bacteria of the coated one is as follows.

Number of bacteria Tetradecyldimethylbenzylammonium salt 0 Dodecyltrimethylammonium salt 0 Number of bacteria Cetylpyridinium salt 0 Benzethonium salt 0 Methylbenzethonium salt 0 Antifungal test 1 A 3 cm square plate made of straight is coated with the following acrylic emulsion-based paint On the paint surface of the obtained test piece,
A methanol solution containing about 10% of tetradecyldimethylbenzylammonium alginate obtained in the above Production Example was sprayed, and then methanol was evaporated to form a film of the above quaternary ammonium alginate salt.

A mold resistance test was conducted using two test pieces of this product and a blank on which a quaternary ammonium alginate salt coating was not formed. That is, a test piece was placed in the center of a potato dextrose agar medium, and Aspergillus niger ATCC 6275, Aspergillus flavus ATCC 9643, Penicillium luteum ATCC 964
4, Trichoderma T-1 ATCC 9645 4
Mold spore suspension of seeds (adjusted according to JIS Z-2911,1981)
Was spray-inoculated and cultured at 30 ° C.

As a result, as shown in the following table, no mold growth was observed on the paint surface coated with the quaternary ammonium alginate salt.

Antifungal test 2 Regarding the tetradecyldimethylbenzylammonium salt of alginic acid obtained in the production example of quaternary ammonium alginate, the following fungi were used to prevent the fungus resistance test according to JIS Z-2911-1981. A moldability test was conducted.

50mm x 50mm as a solution of the ammonium salt in methanol
The sample was impregnated with the filter paper of No. 1 and then dried to prepare the samples shown in Table 1.

A sample is placed on a plate medium and a mold spore suspension is placed on it.
1 ml was evenly sprayed, covered, and cultured at 30 ° C. for 2 weeks. The results obtained and the method for indicating mold resistance are respectively
The results are shown in Table 3 and Table 3.

The spore suspension was obtained by culturing the test bacterium in a potato dextrose agar slant medium and dispersing the obtained spores in sterile water containing 0.005% dioctyl sodium sulfosuccinate.

The composition of the plate medium is as follows.

Purified water 1000 ml, potassium chloride 0.25 g ammonium nitrate 3.0 g, ferrous sulfate 0.002 g, phosphoric acid-potassium 1.0 g agar 25 g and magnesium sulfate 0.5 g.

(F) Effect of the Invention According to the present invention, it is possible to easily impart a persistent antifungal bactericidal property to equipment and materials of equipment particularly required for antifungal bactericidal property.

Claims (1)

[Claims] 1. A quaternary ammonium salt of alginic acid, comprising:
The carboxy residues of D-mannuronic acid and L-guluronic acid, which are the constituent units of alginic acid, are represented by the following formula: (In the formula, R ^{1 to} R ⁴ are each a C _1-20 linear or branched saturated or unsaturated aliphatic hydrocarbon group,
Three of R ^{1 to} R ⁴ are the above hydrocarbon groups and one is an aralkyl group,
A trialkylammonium alkyl group or an aryloxyalkyl group, two of R ^{1 to} R ⁴ are the above hydrocarbon groups and the remaining two aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or R ^{1 to} R ⁴ are one or two of the above hydrocarbon groups and the remaining two or three form a heterocyclic ring with a nitrogen atom), and are particularly water-insoluble or insoluble quaternary ammonium alginate salts. The organic solvent or a solution of a mixture of an organic solvent and a small amount of water is applied to or impregnated with an object to be imparted with antifungal sterilization property, and then the solvent is removed to prevent the object from antifungal sterilization. A fungicidal sterilization method comprising imparting properties.